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| United States Patent |
5,043,308
|
|
Luetkens, Jr.
, et al.
|
*
August 27, 1991
|
Crystalline rare earth aluminum borates
Abstract
The preparation, structure, and properties of solid inorganic materials
containing at least one rare earth element, aluminum, boron and oxygen are
described. Also described is the use of such materials in catalytic
compositions for the conversion of organic compounds. In particular, new
materials comprising crystalline LnAl.sub.1.67+0.67X (B.sub.4
O.sub.10)O.sub.X where Ln is at least one Group IIIB element ion having
effective ionic radii less than about 0.98 Angstroms at valence 3+ and
coordination number VI, and X is a number ranging from 0 to 1, having a
characteristic X-ray diffraction pattern are described as well as the use
of such materials in various catalyzed processes including oxidative
dehydrogenation of hydrocarbons and oxygen-containing hydrocarbons,
dehydrogenation to functionalize alkylaromatic compounds, and ammoxidation
of alkylaromatic compounds. Also, these new crystalline rare earth
aluminum borates exhibit a variety of physical properties that make their
use as optical materials attractive, including uses for optical frequency
conversion, fluorescence, and laser materials.
| Inventors:
|
Luetkens, Jr.; Melvin L. (Batavia, IL);
Satek; Larry C. (Wheaton, IL)
|
| Assignee:
|
Amoco Corporation (Chicago, IL)
|
| [*] Notice: |
The portion of the term of this patent subsequent to February 5, 2008
has been disclaimed. |
| Appl. No.:
|
330418 |
| Filed:
|
March 29, 1989 |
| Current U.S. Class: |
502/204; 252/301.4R; 423/263; 423/277; 423/279; 558/320; 558/327; 585/443; 585/444; 585/486; 585/658 |
| Intern'l Class: |
B01J 021/02; C01F 017/00; C01B 035/12 |
| Field of Search: |
423/277-279,213.2,600,263
502/202,204,207
585/443,658,444,486
558/320,327
252/301.4 R
|
References Cited
U.S. Patent Documents
| 2118143 | May., 1938 | Benner et al. | 423/279.
|
| 3057677 | Oct., 1962 | Ballman | 423/277.
|
| 3080242 | Mar., 1963 | Berry | 423/277.
|
| 3350166 | Oct., 1967 | Alley et al. | 423/279.
|
| 3856702 | Dec., 1974 | McArthur | 423/279.
|
| 3856705 | Dec., 1974 | McArthur | 423/279.
|
| 3860692 | Jan., 1975 | Nies et al. | 423/277.
|
| 4024171 | May., 1977 | McArthur | 423/213.
|
| 4246246 | Jan., 1981 | Nakamura | 423/279.
|
| 4645753 | Feb., 1987 | Zletz et al. | 423/279.
|
| 4656016 | Apr., 1987 | Taramasso et al. | 423/277.
|
| 4729979 | Mar., 1988 | Zletz | 423/279.
|
| 4766102 | Aug., 1988 | Satek et al. | 423/600.
|
| 4767738 | Aug., 1988 | Melquist et al. | 423/277.
|
| 4990480 | Feb., 1991 | Luetkens, Jr. et al. | 502/204.
|
| Foreign Patent Documents |
| 1072933 | Jun., 1967 | GB | 423/279.
|
Other References
Ballman, A. A., "A New Series of Synthetic Borates Isostructural with the
Carbonate Mineral Huntingtonite", The American Mineralogist 47 (1962), pp.
1380-1383.
Pashkova et al., "A New Series of Double Metaborates", Dokl. Akad. Nauk.
SSSR 258 (1981) pp. 103-106.
Bither et al., "MBO.sub.3 Calcite-Type Borates of Al, Ga, Tl, Rh", J. Solid
State Chem., vol. 6, No. 4 (1973), pp. 502-508.
Leonyuk et al., "Neodymium Incorporation into Y-Al Borate Crystals in
Preparation from Solutions in Molten Potassium Trimolybdate", Krystall und
Technik, vol. 14, No. 1 (1979), pp. 47-50.
Scholze, V. H., "Uber Aluminium borate", Z. anorg. allg. Chemie, vol. 284
(1956), pp. 272-277.
|
Primary Examiner: Breneman; R. Bruce
Attorney, Agent or Firm: Jerome; Frederick S., Magidson; William H., Medhurst; Ralph C.
Claims
We claim:
1. A crystalline material comprising aluminum, boron, oxygen and at least
one element selected from the group consisting of Group IIIB of the
Periodic Table having effective ionic radii less than 0.98 Angstroms at
valence 3+ and coordination number VI having an X-ray diffraction pattern
comprising significant lines substantially as set forth below:
______________________________________
Interplanar
Spacing d, Assigned
Angstroms Strength
______________________________________
9.15 .+-. 0.25 Medium-Strong
4.57 .+-. 0.15 Weak-Medium
3.62 .+-. 0.10 Very Strong
2.98 .+-. 0.08 Strong
2.41 .+-. 0.05 Weak
2.28 .+-. 0.05 Weak
1.98 .+-. 0.04 Weak
1.82 .+-. 0.04 Weak"
______________________________________
2. The composition of claim 1 and a binder.
3. The composition of claim 1 comprising the crystalline material and from
about 0.05 to about 50 wt % of at least one metallo element selected from
the group consisting of Groups IA, IIA, IIB, VIB and VIII of the Periodic
Table based on the weight of crystalline material.
4. The composition of claim 1 wherein the crystalline material has the
empirical formula LnAl.sub.1.67+0.67X (B.sub.4 O.sub.10)O.sub.X, Ln is at
least one rare earth element ion and X is a number ranging from 0 to 1.
5. The composition of claim 4 wherein Ln comprises lutetium.
6. The composition of claim 4 wherein Ln comprises ytterbium.
7. The composition of claim 4 wherein Ln comprises thulium.
8. The composition of claim 4 wherein Ln comprises erbium.
9. The composition of claim 4 wherein Ln comprises holmium.
10. The composition of claim 4 wherein Ln comprises yttrium.
11. The composition of claim 4 wherein Ln comprises dysprosium.
12. The composition of claim 4 wherein Ln comprises terbium.
13. The composition of claim 4 wherein Ln comprises gadolinium.
14. The composition of claim 4 wherein Ln comprises europium.
15. The composition of claim 4 wherein Ln comprises samarium.
16. The composition of claim 4 wherein Ln comprises promethium.
17. The composition of claim 5 wherein the crystalline material has the
empirical formula LuAl.sub.2 B.sub.4 O.sub.10.5
18. The composition of claim 6 wherein the crystalline material has the
empirical formula YbAl.sub.2 B.sub.4 O.sub.10.5
19. The composition of claim 7 wherein the crystalline line material has
the empirical formula TmAl.sub.2 B.sub.4 O.sub.10.5
20. The composition of claim 8 wherein the crystalline material has the
empirical formula ErAl.sub.2 B.sub.4 O.sub.10.5
21. The composition of claim 9 wherein the crystalline material has the
empirical formula HoAl.sub.2 B.sub.4 O.sub.10.5
22. The composition of claim 10 wherein the crystalline material has the
empirical formula YAl.sub.2 B.sub.4 O.sub.10.5
23. The composition of claim 11 wherein the crystalline material has the
empirical formula DyAl.sub.2 B.sub.4 O.sub.10.5
24. The composition of claim 12 wherein the crystalline material has the
empirical formula TbAl.sub.2 B.sub.4 O.sub.10.5
25. The composition of claim 13 wherein the crystalline material has the
empirical formula GdAl.sub.2 B.sub.4 O.sub.10.5
26. The composition of claim 14 wherein the crystalline material has the
empirical formula EuAl.sub.2 B.sub.4 O.sub.10.5
27. The composition of claim 15 wherein the crystalline line material has
the empirical formula SmAl.sub.2 B.sub.4 O.sub.10.5
28. The composition of claim 16 wherein the crystalline material has the
empirical formula PmAl.sub.2 B.sub.4 O.sub.10.5
29. The process of making the crystalline material of claim 1 which
comprises dispersing in a liquid medium a source of alumina, a source of
boria, and a source of at least one Group IIIB element ion selected from
the group consisting of lutetium(III), ytterbium(III), thulium(III),
erbium(III), holmium(III), yttrium(III), dysprosium(III), terbium(III),
gadolinium(III), europium(III), samarium(III), and promethium(III) ions to
form a mixture, removing substantially all the liquid from the mixture to
form a superficially dry solid, and calcining the superficially dry solid
at a temperature in a range from about 600.degree. to about 1500.degree.
C.
30. The process of claim 29, wherein the molar ratio of the source of Group
IIIB element ions to the source of boria, in terms of oxides calculated as
Ln.sub.2 O.sub.3 /B.sub.2 O.sub.3, is about 0.02 to about 1, and the molar
ratio of the source of alumina to the source of boria, in terms of oxides
calculated as Al.sub.2 O.sub.3 /B.sub.2 O.sub.3, is about 0.1 to about 4.
31. The process of claim 30, wherein the Ln.sub.2 O.sub.3 /B.sub.2 O.sub.3
molar ratio is about 0.05 to about 0.82, the Al.sub.2 O.sub.3 /B.sub.2
O.sub.3 mole ratio is about 0.25 to about 2.33, and the pH of the mixture
is in a range from about 2 to about 10.
32. The process of making the crystalline material of claim 5, which
comprises forming an aqueous composition comprising a source of
lutetium(III) ions, a source of alumina, and a source of boria, at a pH in
a range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
33. The process of making the crystalline material of claim 6, which
comprises forming an aqueous composition comprising a source of
ytterbium(III) ions, a source of alumina, and a source of boria, at a pH
in a range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
34. The process of making the crystalline material of claim 7, which
comprises forming an aqueous composition comprising a source of
thulium(III) ions, a source of alumina, and a source of boria at a pH in a
range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
35. The process of making the crystalline material of claim 8, which
comprises forming an aqueous composition comprising a source of
erbium(III) ions, a source of alumina, and a source of boria, at a pH in a
range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystallinematerial.
36. The process of making the crystalline material of claim 9, which
comprises forming an aqueous composition comprising a source of
holmium(III) ions, a source of alumina, and a source of boria, at a pH in
a range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
37. The process of making the crystalline material of claim 10, which
comprises forming an aqueous composition comprising a source of
yttrium(III) ions, a source of alumina, and a source of boria, at a pH in
a range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
38. The process of making the crystalline material of claim 11 which
comprises forming an aqueous composition comprising a source of
dysprosium(III) ions, a source of alumina, and a source of boria, at a pH
in a range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
39. The process of making the crystalline material of claim 12, which
comprises forming an aqueous composition comprising a source of
terbium(III) ions, a source of alumina, and a source of boria, at a pH in
a range from about 3 to about 9, drying the mixture to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
40. The process of making the crystalline material of claim 13, which
comprises forming an aqueous composition comprising a source of
gadolinium(III) ions, a source of alumina, and a source of boria, at a pH
in a range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
41. The process of making the crystalline material of claim 14, which
comprises forming an aqueous composition comprising a source of
europium(III) ions, a source of alumina, and a source of boria, at a pH in
a range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
42. The process of making the crystalline material of claim 15, which
comprises forming an aqueous composition comprising a source of
samarium(III) ions, a source of alumina, and a source of boria, at a pH in
a range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
43. The process of making the crystalline material of claim 16, which
comprises forming an aqueous composition comprising a source of
promethium(III) ions, a source of alumina, and a source of boria, at a pH
in a range from about 3 to about 9, drying the composition to form a
superficially dry solid, and calcining the dry solid at a temperature in a
range from about 700.degree. to about 1100.degree. C. to form said
crystalline material.
Description
BACKGROUND OF THE INVENTION
The present invention relates to crystalline inorganic materials containing
at least one rare earth element, aluminum, boron and oxygen. In
particular, new materials comprising crystalline LnAl.sub.1.67+0.67X
(B.sub.4 O.sub.10)O.sub.X where Ln is at least one rare earth element ion
having effective ionic radii less than about 0.98 Angstroms at valence 3+
and coordination number VI, and X is a number ranging from 0 to 1, having
a characteristic X-ray diffraction pattern are described as well as the
use of such materials in various catalyzed processes including partial
oxidation and oxidative dehydrogenation of hydrocarbons and
oxygen-containing hydrocarbons, dehydrogenation to functionalize
alkylaromatic compounds, dealkylation of alkylaromatic compounds, and
ammoxidation of alkylaromatic compounds. Also these new crystalline rare
earth aluminum borates exhibit a variety of physical properties that make
their use as optical materials attractive, including uses for optical
frequency conversion, fluorescence, and laser materials.
The use of an active metallo element or a supported metallo element
composition containing aluminum and boron as a conversion catalyst is
known in the art. U.S. Pat. No. 3,883,442 to McArthur is illustrative of
prior art disclosing the superiority of a supported active metal catalyst
to resist shrinkage at high temperatures (up to 1600.degree. C.) by
stabilization of a preformed alumina catalyst support. McArthur states
stabilization was achieved by impregnating an alumina support with a
solution of a boron compound which is thermally decomposable to B.sub.2
O.sub.3, followed by drying and calcining of the impregnated support at
temperatures below about 1500.degree. C., but sufficiently high to
decompose the boron compound. McArthur also discloses that the most
commonly used technique of preparing a supported metallo element catalyst
involved, following calcination, impregnating in conventional manner the
alumina support material containing some retained B.sub.2 O.sub.3 with a
solution of the desired metal salt, preferably those that are thermally
decomposable to give the corresponding metal oxides and/or sulfides, and
calcining the salt-impregnated support to convert the impregnated salt to
the active catalytic form. McArthur neither discloses nor suggests a mixed
oxide composition of a rare-earth element, aluminum, and boron.
In U.S. Pat. No. 3,954,670 to Pine, a boria-alumina based catalyst is
disclosed in the combination of a metallo element and a boria-alumina
catalyst support material prepared by hydrolysis of a mixture of aluminum
alkoxide and boron alkoxide in the presence of water at a temperature in
the range of 20.degree. to 100.degree. C. The disclosed catalyst
compositions, said to be useful for desulfurization, denitrogenation,
reforming and other hydrocarbon conversion processes, included rare earths
such as cesium, lanthanum, neodymium, etc. as metallo elements in
combinations with the boria-alumina catalyst composition disclosed in Pine
and, optionally, a crystalline aluminosilicate zeolite with or without
rare earth elements. However, Pine neither discloses nor suggests any
crystalline mixed oxide composition of a rare-earth element, aluminum, and
boron.
Zletz in U.S. Pat. No. 4,729,979, which is hereby incorporated by
reference, discusses the characteristics of a good catalyst and/or
catalyst support and a new crystalline copper aluminum borate
characterized by a specific X-ray diffraction pattern, surface area and
pore volume which is at least partially reducible with hydrogen at a
temperature no more than 350.degree. C. to a composition containing zero
valent copper and Al.sub.4 B.sub.2 O.sub.9. Satek in U.S. Pat. No.
4,590,324, which is hereby incorporated by reference, discusses using the
new crystalline copper aluminum borate as a catalyst to dehydrogenate
alkylaromatics to alkenylaromatics. Zletz et al. in U.S. Pat. No.
4,645,753, which is hereby incorporated by reference, discusses doping the
new crystalline copper aluminum borate to contain an alkali metal or
alkaline earth metal element for use as a catalyst to dehydrogenate
alkylaromatics to alkenylaromatics. The Zletz, Satek, and Zletz et al.
patents alone or in combination neither disclose nor suggest a mixed oxide
composition of aluminum, boron, and a metallo element without copper.
Furthermore, these patents disclose crystalline copper aluminum borate
having significant X-ray diffraction lines which are substantially
different from X-ray diffraction patterns for crystalline materials of the
present invention.
A. A. Ballman discloses the preparation of rare earth aluminum borates from
a molten solution with the general formula RAl.sub.3 B.sub.4 O.sub.12
where R was yttrium, neodymium, samarium, europium, gadolinium, terbium,
dysprosium, holmium, ytterbium and erbium in American Mineralogist 47,
1380-1383, (1962), "A New Series of Synthetic Borates Isostructural with
the Carbonate Mineral Huntite" which is hereby incorporated by reference.
A molten solution of potassium sulfate and molybdic anhydride (1:3 mole
ratio) or lead fluoride and boric oxide (1:3 mole ratio) were used to
dissolve the component oxides and produced single crystals ranging in size
from about 0.1-10 mm when slowly cooled from 1150.degree. to 900.degree.
C. The rare earth aluminum borates produced by the indicated route are
believed to be well-defined, dense crystalline particles which have an
extremely low surface area due to heating a mixture of oxides to a
temperature of 1150.degree. C. Ballman neither discloses nor suggests a
mixed oxide composition of aluminum, boron,, and a rare earth element
having an aluminum to boron ratio less than 3/4 . Furthermore, the
crystalline compounds disclosed by Ballman are characterized by having
significant X-ray diffraction lines which are substantially different from
X-ray diffraction patterns for crystalline materials of the present
invention.
Kong Hua-shuang, Zhang Shou-qing, He Chung-fan and Zhang Dao-biao disclose
the preparation of NdAl.sub.2 (B.sub.4 O.sub.10)O.sub.0.5 crystals grown
from solvent in Research Inorganic Materials, (1982-1983), 10-12, "X-ray
Difin fraction Powder Data and Some Physical Properties of NdAl.sub.2
(B.sub.4 O.sub.10)O.sub.0.5 " which is hereby incorporated by reference. A
molten solution of BaO-B.sub.2 O.sub.3 -NdAl.sub.3 (BO.sub.3).sub.4 was
heated to 1120.degree. C. and maintained at that temperature for 13 hours,
then cooled down to 900.degree. C. at the rate of 20.degree. C./hr by the
authors to obtain "a lot of small and thin crystals." The crystalline
material produced by the indicated route is believed to be well-defined,
dense crystalline particles which have an extremely low surface due to
heating a mixture of oxides to a temperature of 1120.degree. C.
A. V. Pashkova, O. V. Sorokina, N. I. Leonyuk, T. I. Timchenko, and N. V.
Belov, disclose four double metaborates having the general formula
TRAl.sub.1.67+0.67X (B.sub.4 O.sub.10)O.sub.X where TRis lanthanum,
cerium, praseodymium, or neodymium and X varies from 0 to 1, Sov. Phys,
Dokl. 26(5), 457-459 (May 1981). Crystals of these materials were obtained
from solution in a melt of potassium trimolybdate by crystallization in
the form of hexagonal plates at temperatures in the range of 1100.degree.
to 800.degree. C. by smoothly lowering the temperature at a rate of
0.5.degree. to 2.degree. C./hr. The authors state that their attempts to
obtain dimetaborates of other rare earth elements by the same method did
not yield positive results.
In the Pashkova paper, FIG. 2. shows a relationship between unit-cell
parameters of four TRAl-dimetaborates and ionic radius of TR elements
where TR is lanthanum, cerium, praseodymium, or neodymium. The authors
state that, under the given conditions, the borates obtained are stable
only for elements at the beginning of the rare-earth series, i.e., for
elements having ionic radii in a range from the ionic radius of lanthanum
to the ionic radius of neodymium.
The effective ionic radii of Shannon & Prewitt, Acta Cryst. (1969), B25,
925-945, have been revised to include more unusual oxidation states and
coordinations by R. D. Shannon in Acta Cryst. (1976), A32, 751-767,
incorporated herein by reference. Effective ionic radii found in Shannon
for selected elements at valence 3+ and coordination number VI are set out
below.
______________________________________
Effective Ionic Radii
Ion.sup.1 IR.sup.2, .ANG.
______________________________________
Scandium, Sc 0.745
Indium, In 0.800
Lutetium, Lu 0.861
Ytterbium, Yb 0.868
Thulium, Tm 0.880
Erbium, Er 0.890
Holmium, Ho 0.901
Yttrium, Y 0.900
Dysprosium, Dy 0.912
Terbium, Tb 0.923
Gadolinium, Gd 0.938
Europium, Eu 0.947
Samarium, Sm 0.958
Promethium, Pm 0.970
Neodymium, Nd 0.983
Praseodymium, Pr 0.990
Cerium, Ce 1.01
Lanthanum, La 1.032
______________________________________
.sup.1 Ion at valence 3+ and coordination number VI.
.sup.2 Effective ionic radii in Angstroms, .ANG..
The general object of the present invention is to provide new crystalline
materials having chemical and physical characteristics that make them
useful catalytically and/or optically.
Another general object of this invention is to produce a new solid material
which is useful in various catalyzed processes including partial oxidation
and/or oxidative dehydrogenation of hydrocarbons and oxygen-containing
hydrocarbons, in dehydrogenation of alkylaromatic compounds, in
dealkylation of alkyaromatic compounds, and in ammoxidation of
alkylaromatic compounds.
Another general object of this invention is to produce new synthetic
crystalline compositions which are useful as frequency doubling materials
in laser applications, and/or fluorescence materials.
Other objects and advantages of the invention will become apparent upon
reading the following detailed description and appended claims.
SUMMARY OF THE INVENTION
In one aspect, the present invention is a crystalline inorganic material
comprising aluminum, boron, oxygen and at least one element selected from
the group consisting of Group IIIB of the Periodic Table having effective
ionic radii less than about 0.98 Angstroms at valence 3+ and coordination
number VI, the material having an X-ray diffraction pattern comprising
significant lines substantially as described in Table I.
The Periodic Table is the well known arrangement of chemical elements based
on the periodic law and is found in Webster's Ninth New Colleqiate
Dictionary, Merriam-Webster Inc., Springfield, Mass., U.S.A., (1984) at
page 874. Group IIIB elements are scandium, yttrium, the lanthanide series
(elements with atomic numbers 57 through 71) and the actinide series
(elements with atomic numbers 90 through 103). Rare earth elements include
all Group IIIB elements not in the actinide series.
Biphasic crystalline inorganic materials comprising aluminum, boron, oxygen
and at least transition element selected from the group consisting of
Group IIIB of the Periodic Table having an X-ray diffraction pattern
comprising significant lines substantially as described in Table I and
lines identifying crystalline Ln.sub.2 O.sub.3 .multidot.3 Al.sub.2
O.sub.3 4 B.sub.2 O.sub.3 are claimed in commonly assigned application
Ser. No. 330,608 filed on even date in the name of Luetkens and Satek, now
U.S. Pat. No. 4,990,480, which is hereby incorporated by reference. As
indicated below, the catalyst of this invention can be used for conversion
of alcohols to useful organic compounds, such as alkenes, aldehydes,
and/or ketones (this is the subject of commonly assigned application Ser.
No. 330,417, filed on even date in the name of Luetkens et al., now U.S.
Pat. No. 4,929,763, which is hereby incorporated by reference).
In another aspect, the invention describes the preparation and properties
of a crystalline inorganic material comprising aluminum, boron, oxygen,
and at least one Group IIIB element, preferably selected from the group
consisting of rare earth elements having effective ionic radii less than
about 0.98 Angstroms at valence 3+ and coordination number VI, made by
calcining a mixture containing sources of trivalent Group IIIB ions,
alumina, and boria at elevated temperature, the material providing an
X-ray pattern comprising lines substantially as shown in Table I.
In a preferred embodiment, the present invention is an inorganic material
comprising crystalline
LnAl.sub.1.67+0.67X (B.sub.4 O.sub.10)O.sub.X
where Ln is at least one trivalent ion, preferably selected from the group
consisting of Group IIIB of the Periodic Table having effective ionic
radii less than about 0.98 Angstroms at valence 3+ and coordination number
VI, preferably having effective ionic radii in a range from about 0.975 to
about 0.8 Angstroms and more preferably in a range from about 0.97 to
about 0.86 Angstroms, and X is a number ranging from 0 to 1, preferably
about 1/2, the material having an X-ray diffraction pattern comprising
significant lines and assigned strengths substantially as shown in Table
I.
TABLE I
______________________________________
Principal XRD Lines
Interplanar
Spacing d,.sup.1
Assigned
.ANG. Strength.sup.2
______________________________________
9.15 .+-. 0.25
M-S
4.57 .+-. 0.15
W-M
3.62 .+-. 0.10
VS
2.98 .+-. 0.08
S
2.41 .+-. 0.05
W
2.28 .+-. 0.05
W
1.98 .+-. 0.04
W
1.82 .+-. 0.04
W
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
As is generally known, the assigned strengths in X-ray diffraction patterns
may vary depending upon the characteristics of the sample. The observed
line strangth in any particular sample may vary from another sample. Also,
X-ray diffraction lines of a particular crystalline material may be
obscured by lines from other materials present in a measured sample.
Preferred embodiments include crystalline material having the following
empirical formulas:
______________________________________
LuAl.sub.2 B.sub.4 O.sub.10.5,
YbAl.sub.2 B.sub.4 O.sub.10.5,
TmAl.sub.2 B.sub.4 O.sub.10.5,
ErAl.sub.2 B.sub.4 O.sub.10.5,
HoAl.sub.2 B.sub.4 O.sub.10.5,
YAl.sub.2 B.sub.4 O.sub.10.5,
DyAl.sub.2 B.sub.4 O.sub.10.5,
TbAl.sub.2 B.sub.4 O.sub.10.5,
GdAl.sub.2 B.sub.4 O.sub.10.5,
EuAl.sub.2 B.sub.4 O.sub.10.5,
SmAl.sub.2 B.sub.4 O.sub.10.5, and
PmAl.sub.2 B.sub.4 O.sub.10.5.
______________________________________
Another aspect of the invention describes the preparation and properties of
a crystalline material having an X-ray diffraction pattern comprising
significant lines substantially as described in Table I and the chemical
composition
Ln.sub.2 O.sub.3 .multidot.(m) Al.sub.2 O.sub.3 .multidot.(n) B.sub.2
O.sub.3
where Ln is at least one metallo element selected from the group consisting
of Group IIIB of the Periodic Table having effective ionic radii less than
about 0.98 Angstroms at valence 3+ and coordination number VI, and where m
and n are numbers representing molar amounts of the oxides such that ratio
n/m is in a range from about 0.25 to about 9, preferably about 0.42 to
about 4, and more preferably about 2.
In still another aspect, the invention describes the use of such solid
materials in catalytic compositions for the chemical conversion of organic
compounds. In a further aspect, the invention describes the use of such
materials for dehydrogenation and/or dehydration of hydrocarbons and
oxygen-containing hydrocarbons, for example in the conversion of alkanes
and/or alcohols to the corresponding alkenes and other useful organic
compounds. In a further aspect, the invention describes the use of such
materials for dehydrogenation and/or dealkylation of alkylaromatic
compounds. In a further aspect, the invention describes the use of such
materials for ammoxidation of alkylaromatic compounds.
In another aspect, the invention describes the use of such solid materials
as frequency doubling material for laser applications. In a further
aspect, the invention describes the use of such solid materials as
fluorescent materials.
DETAILED DESCRIPTION OF THE INVENTION
The rare-earth, aluminum, boron, and oxygen solid materials of the present
invention can be prepared by calcining a mixture of a source of
lutetium(III), ytterbium(III), thulium(III), erbium(III), holmium(III),
yttrium(III), dysprosium(III), terbium(III), gadolinium(III),
europium(III), samarium(III), and/or promethium(III) ions, a source of
alumina, and a source of boria.
Conditions of calcination include a temperature within the range of about
600.degree. C. to about 1500.degree. C., a pressure of at least about one
atmosphere, and a reaction time that is sufficient to effect formation of
a crystalline metalloaluminum borate. Increasing pressure and temperature
of calcination, generally affect formation of a crystalline
metalloaluminum borate in a shorter reaction time. However, a high
temperature of calcination typically results in crystalline materials with
less desirably surface properties, for example low surface area. Preferred
calcination temperatures are in a range of about 700.degree. C. to
1100.degree. C. Calcination can be carried out in air, nitrogen or other
inert gases. A preferred atmosphere for calcination contains oxygen.
The solid materials of this invention can be prepared generally by
dispersing the required ingredients in a liquid medium, preferably an
aqueous medium, removing substantially all the liquid to form
superficially dry mixture, and calcining the dry mixture.
When a liquid medium is used, the source of Group IIIB element ions can be
a sol or any reasonably soluble salt of lutetium(III), ytterbium(III),
thulium(III), erbium(III), holmium(III), yttrium(III), dysprosium(III),
terbium(III), gadolinium(III), europium(III), samarium(III),
promethium(III) ions, or precursor thereof which is at least partially
soluble in the dispersing liquid, such as the acetate, formate, nitrate,
carbonate, chloride, bromide, sulfate and the like. Salts of rare earth
elements containing a decomposable anion such as yttrium nitrate, yttrium
acetate, yttrium formate, yttrium carbonate, ytterbium(III) nitrate,
ytterbium(III) acetate, ytterbium(III) formate, ytterbium(III) carbonate,
etc. are preferred. When the source of Group IIIB element is a sol, oxides
are preferred.
Typically, best results are obtained when each of the sources used is
chosen to reduce the content of foreign anions and cations in the reaction
mix.
The source of alumina is any material capable of producing alumina, but
preferred is a well dispersed, liquid source such as an alumina sol.
The source of boria is a material such as borate or boric acid with pure
boric acid being preferred.
Typically, the mole ratios of the various reactants can be varied to
produce the solid of this invention. Specifically, the mole ratios in
terms of oxides of the initial reactant concentrations are characterized
by the general mixed oxide formula
(x) Ln.sub.2 O.sub.3 .multidot.(y) Al.sub.2 O.sub.3 .multidot.(z) B.sub.2
O.sub.3
where x, y and z are numbers eepresenting molar amounts of the oxides of
the source reagents.
The mole ratios of Ln.sub.2 O.sub.3 /B.sub.2 O.sub.3, calculated as x/z,
are about 0.02 to about 1, preferably about 0.05 to about 0.82, and most
preferably about 0.10 to about 0.50, and the mole ratios of Al.sub.2
O.sub.3 /B.sub.2 O.sub.3, calculated as y/z, are from about 0.1 to about
4, preferably about 0.25 to about 2.33, and more preferably about 0.33 to
about 2.
In somewhat greater detail, a preferred procedure is to dissolve the boria
source and disperse the alumina source in water with mixing in a blender
for about 3-5 minutes, then add an aqueous sol or solution of a source of
a Group IIIB element to the blender followed by gelation with ammonia.
Typically, the pH of the aqueous mixture is less than about 11. If the
reaction media is too acid or too basic, the desired solid generally will
not form or other contaminating phases are formed in addition to the
desired product. To some extent the pH of the reaction mixture controls
surface properties of the final calcined solid material. Preferably, the
pH of the reaction mixture is in a range from about 2 to about 10, more
preferably about 3 to about 9, in order to gel the reaction mixture. If
desired, the pH can be adjusted with a base such as ammonia,
ethylenediamine, tetramethylammonium hydroxide and the like. Preferred is
the use of ammonium hydroxide. The presence of the ammonia as well as
other volatile components in the gelled mixture, such as acetate ion,
nitrate ion, etc., is advantageous in providing the final calcined solid
with sufficiently high surface area and porosity desirable for catalytic
reactions.
The gelled mixture is allowed to air-dry, usually for about 1-3 days,
followed by vacuum drying, typically at a pressure of about 0.3 atmosphere
for about 15 to 25 hours at about 100.degree. C. to 150.degree. C. with a
purge of dry gas, such as nitrogen.
The superficially dry mixture is calcined, preferably at a temperature
within the range of about 700.degree. to about 1100.degree. C. for a
reaction time that is sufficient to effect formation of a crystalline
metalloaluminum borate, typically a reaction time within the range of
about 2 to about 30 hr. Samples of material can be removed during
calcination to check the degree of crystallization and determine the
optimum calcination time.
The crystalline material formed can be crushed to a powder or to small
particles and extruded, pelletized, or made into other forms suitable for
its intended use. In a preferred embodiment of the above-described method,
the crystalline material formed can be washed with a solvent, preferably
an aqueous solvent, which removes impurities such as excess boria, without
destroying the crystalline material formed, mildly dried for anywhere from
a few hours to a few days at varying temperatures, typically about
50.degree. to about 225.degree. C., to form a dry cake which can then be
treated as required for its intended use.
The solid materials made by this invention can be admixed with or
incorporated within various binders or matrix materials depending upon the
intended process use. They are combined with active or inactive materials,
synthetic or naturally occurring oxides, as well as inorganic or organic
materials which would be useful for binding such substances. Well-known
materials include silica, silica-alumina, alumina, magnesia, titania,
zirconia, alumina sols, hydrated aluminas, clays such as bentonite or
kaolin, Sterotex (a powdered vegetable stearine produced by Capital City
Products, Co., Columbus, Ohio), or other binders well known in the art.
Advantageously, a crystalline material formed according to this invention
is formed or combined with from about 0.05 to about 50 wt % of at least
one compound of a metallo element selected from the group consisting of
Groups IA, IIA, IIB, VIB and VIII of the Periodic Table based on the
weight of crystalline material.
Suitable alkali metal (Group IA), alkaline earth metal (Group IIA), low
melting metal (Group IIB) brittle metal (Group VIB), and heavy metal
(Group VIII) compounds include the oxides, hydroxides and salts of
lithium, sodium, potassium, rubidium, cesium, magnesium, calcium,
strontium, barium, chromium, zinc, cadmium, lanthanum, cerium, and
thorium, such as lithium hydroxide, sodium hydroxide, potassium hydroxide,
magnesium hydroxide, potassium oxide, sodium oxide, potassium carbonate,
sodium carbonate, sodium bicarbonate, potassium nitrate, potassium borate,
sodium borate, potassium chloride, potassium acetate, sodium propionate,
potassium maleate, etc. Of these, potassium and chromium, in the form of
the oxide or in a form readily convertible to the oxide, are preferred.
The solid materials formed according to this invention can be treated with
from about 0.05 to 50 wt % dopant based on the weight of the solid
material. The metallo compound or compounds can be dry-blended with the
aluminum borate, dissolved in a suitable solvent, preferably water, mixed
with the solid material and dried; or aqueous solutions of same can be
added to feedstocks going to a reactor containing the solid material
catalyst.
Catalyst compositions of this invention are useful generally in the
chemical conversion of organic compounds, particularly hydrocarbon and
oxygenated hydrocarbon. In particular, chemical conversion reactions such
as oxidation, dehydration, dehydrogenation, oxidative dehydrogenation,
dealkylation, and ammoxidation have been carried out. Crystalline
materials of this invention have been used for oxidation of ethanol to
acetaldehyde and/or acetic acid, for dehydration of ethanol to ethylene
and 2-butanol to C.sub.4 olefins and/or methyl ethyl ketone, for
dehydrogenation of cumene to alpha-methylstyrene, for oxidative
dehydrogenation of propane to propylene, and for ammoxidation of toluene
to benzonitrile.
Particularly useful is the fact that when these solid catalyst compositions
are used in liquid and/or gas phase processes, the products of chemical
conversion are easily separated from the solid catalyst material. Also
useful is the fact that when these solid catalyst compositions are used in
such fluid-phase processes, the active metallo element components are only
slowly extracted, leading to longer catalyst lifetime.
Generally a process of the present invention for chemical conversion
comprises contacting under suitable reaction conditions an organic
reactant in a fluid phase, i.e., liquid and/or vapor phase, with a
heterogeneous catalyst composition comprising a crystalline material
having an X-ray diffraction pattern comprising significant lines
substantially as described in Table I and a chemical composition
(x) Ln.sub.2 O.sub.3 .multidot.(y) Al.sub.2 O.sub.3 .multidot.(z) B.sub.2
O.sub.3
where x, y and z are numbers representing molar amounts of the oxides and
Ln is at least one metallo element selected from the group consisting of
Group IIIB of the Periodic Table, preferably selected from the group
consisting of rare earth elements and more preferably selected from the
group consisting of lutetium, ytterbium, thulium, erbium, holmium,
yttrium, dysprosium, terbium, gadolinium, europium, samarium, and
promethium.
The following examples will serve to illustrate certain specific
embodiments of the herein disclosed invention. These examples should not,
however, be construed as limiting the scope of the novel invention, as
there are many variations which may be made thereon without departing from
the spirit of the disclosed invention, as those of skill in the art will
recognize.
For example, ammoxidation processes are well known in the art and numerous
processes with and without added oxygen and with numerous catalysts are
described in various U.S. and foreign patents and publications.
The ammoxidation process of this invention is carried out in either a fixed
bed mode of operation or in a fluidized bed at a temperature between about
375.degree. and 500.degree. C., preferably 400.degree. to 459.degree. C.,
most preferably about 425.degree. to 435.degree. C. The source of oxygen
is preferably air, but any oxygen source is suitable. The amount of oxygen
used in the process may vary over wide limits, but the process enables
rather limited amounts of oxygen to be used and this, in turn, is
favorable in that less burn of hydrocarbon reactant occurs. Thus, the
ratio of oxygen to hydrocarbon in the reactant stream will usually be up
to about 6:1, although it is preferable to use no more than about 3:1,
preferably 2.5:1 to 3:1, although about 2.0:1 is also quite useful.
Likewise the ratio of ammonia to hydrocarbon used in the process of the
invention will be preferably about 3:1, or less, most preferably 2.0:1 to
3:1 although higher ratios, up to 6:1 are also useful. It is also to be
understood that the volume percent concentration of reactants in the feed
may be quite high as compared to most ammoxidation procedures and the feed
may comprise in percent by volume 5 to 25% hydrocarbon, 6 to 20% oxygen,
and 6 to 35% ammonia. In the preferred method, the volume percent
concentration of reactants corresponding to the above preferred ratios
will comprise in percent by volume from about 5 to about 7% toluene, from
about 15 to about 20% oxygen, and from about 10 to about 20% ammonia. The
fact that the process of this invention makes possible this high
concentration of reactants is significant in contributing to a very
efficient overall process.
As indicated, the hydrocarbon reactant will be an alkyl (preferably lower
alkyl; e.g., 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl)
substituted aromatic hydrocarbon and will be preferably of the benzene and
naphthalene series. Most preferably, a member of the benzene series will
be used such as toluene and meta- and para-xylene. When using m-xylene to
obtain isophthalonitrile, however, it is preferred to employ temperatures
at the lower end of the range given above and this is in accord with art
knowledge that m-xylene is more sensitive to carbon oxide formation than
is the p-isomer.
It will be understood that the contact time for the reactants over the
catalyst will vary over a wide range, but will usually be from about 0.1
to 20 seconds. The contact time actually used will depend upon catalyst
loading, catalyst volume, temperature and other parameters and the skilled
art worker will have no difficulty in selecting an appropriate contact
time dependent upon these reaction parameters.
The reactant feed stream will, of course, contain other materials, as for
example, the inert ingredients of air, recycled intermediates (e.g., a
mononitrile when a dinitrile is desired) and possibly some small amounts
of other by-products associated with the recycle stream. This use of a
recycle stream will make possible a still more efficient process.
In addition to the above required parameters of the process it is essential
that a particular type of material be used as catalyst. Preferred is a
heterogeneous catalyst composition comprising a crystalline material
having an X-ray diffraction pattern comprising significant lines
substantially as described in Table I and chemical composition
Ln.sub.2 O.sub.3 .multidot.(m) Al.sub.2 O.sub.3 .multidot.(n) B.sub.2
O.sub.3
where Ln is at least one metallo element selected from the group consisting
of Group IIIB of the Periodic Table having effective ionic radii less than
about 0.98 Angstroms at valence 3+ and coordination number VI, and where m
and n are numbers representing molar amounts of the oxides such that ratio
n/m is in a range from about 0.25 to about 9, preferably about 0.42 to
about 4, and more preferably about 2.
EXAMPLES
General
Temperatures are in degrees Celsius.
Percents are weight percents.
Rare earth nitrates were obtained from Aldrich Chemical Co., Milwaukee,
Wisc., and/or Strem Chemicals Inc., Newburyport, Mass., at 99.9% purities
and were used in the following examples as received.
The percents of the Ln.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3
.multidot.4 B.sub.2 O.sub.3 phase and the Ln.sub.2 O.sub.3 .multidot.3
Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3 phase in a crystalline
material were based upon relative intensity of X-ray diffraction lines at
interplanar spacing 3.62.+-.0.10 Angstroms and 2.69.+-.0.10 Angstroms.
Samples of crystalline material from particular examples were prepared for
testing as a catalyst by admixing with alpha alumina, an inert diluent.
This mixture of solids was then supported on a bed of alpha alumina and a
glass wool plug in a 6 mm OD.times.19 cm long vycor reactor tube. The
reactor tube was heated to the appropriate temperature with a small
electric furnace (Tracor). Oxygen was supplied to the reactor diluted to
about 8% with nitrogen and at atmospheric pressure. Gas flows from 0.01 to
0.6 mL/sec, were controlled by Brooks Flow Controllers. The reactor
effluent passed through a heated Carle sampling valve which allowed for
direct injections onto a 6 ft. OV17 GC column. Organic products were
analyzed using a FID detector and the fixed gases (i.e., O.sub.2, H.sub.2,
CO, CO.sub.2) were analyzed off-line by GC using a CTR I column (All-tech)
and a TC detector.
EXAMPLE 1
A crystalline lutetium aluminum borate was prepared as follows: Boric acid
(29.7 g, 0.48 mol) dissolved in 148 mL warm deionized water, PHF alumina
sol 129.9 g of 9.5% alumina, 0.12 mol) and Lu(NO.sub.3).sub.3 -3H.sub.2 O
(49.8 g, 0.12 mmol) dissolved in 25 mL warm deionized water were placed
into a blender. This aqueous mixture was blended at a low speed setting to
obtain a smooth white thin gel. The pH of the gel measured 4. Addition of
3 mL of NH.sub.4 OH produced a thixotropic white gel, the pH of which
measured 6. The gel was spread onto a 35 cm.times.45 cm plastic tray and
air-dried to a white solid, 85.9 g, which was vacuum-dried at 0.3 atm
pressure and 120.degree. C. overnight. A 17.9 g portion of the
vacuum-dried material was calcined using the following program:
##STR1##
The hard white chunky calcined material weighed 11.7 g and emitted
fluorescence when illuminated by U.V. Analysis of this crystalline
lutetium aluminum borate by powder X-ray diffraction found about 65
percent Lu.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2
O.sub.3 and about 35 percent Lu.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3
.multidot.4 B.sub.2 O.sub.3.
The powder X-ray diffraction lines of this crystalline lutetium aluminum
borate are set out below:
______________________________________
XRD Lines for Example 1
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.05 VW 4
4.52 VW 7
4.06 M 25
3.91 VW 4
3.73 M 36
3.59 S 45
3.43 VS 99
2.96 M 40
2.92 M 41
2.62 S 83
2.43 W 15
2.39 W 18
2.26 W 13
2.04 W 18
1.98 M 30
1.96 W 24
1.91 VW 7
1.81 M 39
1.77 M 33
1.74 W 18
1.64 VW 4
1.58 W 15
1.55 VW 12
1.48 VW 10
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
EXAMPLE 2
A crystalline ytterbium aluminum borate was prepared as follows: A hot
solution of boric acid (32.8 g, 0.54 mol, a 10% excess) in 200 mL
distilled water was added to alumina sol (149.3 g of a 8.2% alumina sol,
0.12 mol) in a Waring blender while mixing. To this was added solid
Yb.sub.2 O.sub.3 (23.6 g, 0.059 mol). After an additional period of
mixing, 5 mL of dilute (1:1) nitric acid was added to mixture to obtain a
homogeneous white gel. The gel was spread out onto a 35 cm.times.45 cm
plastic tray, air-dried, then dried vacuum-dried at 120.degree. C., and
pre-calcined to 400.degree. C. A portion of this material was calcined at
950.degree. C. Analysis of the resulting crystalline ytterbium aluminum
borate by powder X-ray diffraction found about 90+ percent Yb.sub.2
O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3. The
powder X-ray diffraction lines of the crystalline ytterbium aluminum
borate are set out below:
______________________________________
XRD Lines for Example 2
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.16 S 72
4.56 M 31
3.94 W 16
3.61 VS 100
2.98 S 67
2.40 M 28
2.27 W 19
2.20 VW 11
2.03 VW 11
1.97 W 24
1.92 W 16
1.82 W 22
1.81 W 19
1.52 VW 5
1.49 VW 5
1.47 VW 5
1.42 VW 9
1.41 VW 9
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
EXAMPLE 3
Another example of crystalline ytterbium aluminum borate was prepared as
follows: Boric acid (25.2 g, 0.408 mol) dissolved in 120 mL hot deionized
water, PHF alumina sol (190.6 g of 8.2% alumina, 0.153 mol) and
Yb(NO.sub.3).sub.3 -5H.sub.2 O (45.8 g, 0.102 mol) dissolved in 50 mL
deionized water were placed into a blender. The aqueous mixture was
blended at a low setting, and 24 mL ammonium hydroxide was added to the
aqueous mixture which became a gel. After further blending for several
minutes, the gel was placed onto a 35 cm.times.45 cm plastic tray and
air-dried, then vacuum dried (0.3 atm, 110.degree. C.), and calcined
according to the following program:
##STR2##
Analysis of this white crystalline lutetium aluminum borate by powder X-ray
diffraction found about 70 percent Yb.sub.2 O.sub.3 .multidot.2 Al.sub.2
O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about 30 percent Yb.sub.2 O.sub.3
.multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3. The BET surface
area of this material was determined to be 3.1 m.sup.2 /g.
EXAMPLE 4
A 1 cc sample of ytterbium aluminum borate from Example 3 (18-35 mesh
powder) was prepared for testing as a catalyst by admixing with 0.3 mL of
18/35 mesh alpha alumina, an inert diluent. This mixture of solids was
then tested by the procedure described hereinabove. Initially, the
catalyst was conditioned for one hour at 300.degree. C. under nitrogen,
and for one hour at 500.degree. C. under nitrogen.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and an ethanol flow of 0.00234 mL/min the results were:
Conversion of ethanol 99%
Selectivity to ethylene 89%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and a 2-butanol flow of 0.00234 mL/min the results were:
Conversion of 2-butanol 98%
Selectivity to C.sub.4 olefins 98%
At a temperature of 600.degree. C., a gas flow (8% oxygen in nitrogen) of
0.321 mL/sec, an ammonia flow of 0.013 mL/sec, and a liquid toluene flow
of 0.00234 mL/min the results were:
Conversion of toluene 18%
Selectivity to benzcnitrile 85%
At a temperature of 600.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and a propane flow of 0.0094 mL/sec the results were:
Conversion of propane 12%
Selectivity to propene 89%
EXAMPLE 5
Another example of crystalline ytterbium aluminum borate was prepared as
follows: Boric acid (10.0 g, 0.162 mol) dissolved in 50 mL hot deionized
water, PHF alumina sol (403.5 g of 8.2% alumina, 0.324 and
Yb(NO.sub.3).sub.3 -5H.sub.2 O (24.2 g, 0.054 mol) dissolved in 50 mL
deionized water were placed into a blender. This aqueous mixture was
blended at a low setting, and 14 mL ammonium hydroxide was added to the
aqueous mixture which then became a thick, white gel. After further
blending for several minutes, the gel was air-dried to a solid,
vacuum-dried (0.3 atm, 110.degree. C.), and calcined according to the
following program:
##STR3##
Analysis of this white ytterbium aluminum borate of low crystallinity by
powder X-ray diffraction found 95+ percent crystalline Lu.sub.2 O.sub.3
.multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3. The BET surface
area of this material was determined to be 24 m.sup.2 /g.
EXAMPLE 6
A 0.66 g sample of crystalline ytterbium aluminum borate from Example 5
(18-35 mesh powder) compound was prepared for testing as a catalyst by
admixing with 0.3 mL of 18/35 mesh alpha alumina, an inert diluent. This
mixture of solids was then tested by the procedure described hereinabove.
Initially, the catalyst was conditioned for one hour at 300.degree. C.
under nitrogen, and for one hour at 500.degree. C. under nitrogen.
At a temperature of 600.degree. C., a gas flow (8% oxygen in nitrogen) of
0.321 mL/sec, and a liquid toluene flow of 0.00234 mL/min the results
were:
Conversion of toluene 6%
Selectivity to benzene 80%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.321 mL/sec, an ammonia flow of 0.013 mL/sec, and a liquid toluene flow
of 0.00234 mL/min the results were:
Conversion of toluene 15%
Selectivity to benzonitrile 96%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and an ethanol flow of 0.00234 mL/min the results were:
Conversion of ethanol 88%
Selectivity to ethylene 45%
At a temperature of 400.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and a 2-butanol flow of 0.00234 mL/min the results were:
Conversion of 2-butanol 100%
Selectivity to C.sub.4 olefins 91%
EXAMPLE 7
A crystalline thulium aluminum borate was prepared as follows: Boric acid
(16.3 g, 0.264 mol) dissolved in 70 mL warm deionized water, PHF alumina
sol (79.3 g of 8.6% alumina, 0.067 mol) were placed into a blender, and
Tm(NO.sub.3).sub.3 -5H.sub.2 O (30.0 g, 0.067 mol) added directly to the
aqueous mixture by rinsing out six 5.00 g containers with 10 mL deionized
water. The aqueous mixture was blended at a low setting to obtain a smooth
white thixotropic gel the pH of which measured 5. The gel was placed onto
a 35 cm.times.45 cm plastic tray and air-dried. The white solid, 47.3 g,
was vacuum-dried overnight (0.3 atm, 120.degree. C.) resulting a material
which weighed 35.2 g. A 9.8 g portion of the material was calcined using
the following program:
##STR4##
The calcined material weighed 6.3 g and emitted fluorescence when
illuminated by U.V. Analysis of this crystalline thulium aluminum borate
by powder X-ray diffraction found about 60 percent Tm.sub.2 O.sub.3
.multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about 40
percent Tm.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2
O.sub.3. The powder X-ray diffraction lines of the crystalline thulium
aluminum borate are set out below:
______________________________________
XRD Lines for Example 7
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.08 S 87
5.30 VW 10
4.55 M 34
4.14 M 36
3.92 W 17
3.60 VS 100
3.46 S 87
3.25 VW 12
3.18 S 56
2.97 S 71
2.65 S 71
2.61 W 21
2.40 M 29
2.27 W 15
2.20 VW 8
2.00 VW 12
1.97 W 14
1.92 W 13
1.82 W 23
1.80 M 26
1.78 W 17
1.73 VW 5
1.60 VW 7
1.42 VW 6
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
EXAMPLE 8
A crystalline erbium aluminum borate was prepared as follows: A hot
solution of boric acid (32.8 g, 0.54 mol, a 10% excess) in 200 mL
distilled water was added to alumina sol (149.3 g of a 8.2% alumina sol,
0.12 mol) in a Waring blender while mixing. To this was added a hot
solution containing Er(NO.sub.3).sub.3 -5H.sub.2 O (53.2 g, of distilled
water. After thorough mixing, 15 mL of dilute (1:1) nitric acid was added
to obtain a homogeneous gel. Mixing was continued until a smooth and
uniform pink gel was obtained. The gel was air-dried, vacuum-dried at
120.degree. C. and pre-calcined to 400.degree. C. A portion of this
material was calcined at 900.degree. C. Analysis of this crystalline
erbium aluminum borate by powder X-ray diffraction found about 90 percent
Er.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3.
The powder X-ray diffraction lines of the resulting crystalline erbium
aluminum borate are set out below:
______________________________________
XRD Lines for Example 8
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
8.98 W 25
4.54 W 18
3.92 VW 9
3.61 VS 100
2.98 S 71
2.41 W 24
2.27 W 16
2.21 VW 9
2.03 W 17
1.82 M 31
1.81 M 31
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
Another example of crystalline erbium aluminum borate was prepared as
follows: Boric acid (b 25.7 g, 0.416 mol) dissolved in 93 mL hot deionized
water, PHF alumina sol (241.1 g of 6.6% alumina, 0.156 mol) and
Er(NO.sub.3).sub.3 -5H.sub.2 O (23.1 g, 0.052 mol) dissolved in 93 mL
deionized water were placed into a blender. The aqueous mixture was
blended at a low setting, and 4 mL ammonium hydroxide was added to the
aqueous mixture which then became a thick gel, light pink in color. After
further blended for several minutes the gel was air-dried, vacuum-dried
for 72 hours (0.3 atm, 110.degree. C.), and calcined according to the
following program:
##STR5##
Analysis of this pink erbium aluminum borate by powder X-ray diffraction
found about 40 percent Er.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3
.multidot.4 B.sub.2 O.sub.3 and about 60 percent Er.sub.2 O.sub.3
.multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3. The BET surface
area of this material was determined to be 1.7 m.sup.2 /g.
EXAMPLE 10
A 0.68 g sample of crystalline erbium aluminum borate from Example 9 (18-35
mesh powder) was prepared for testing as a catalyst by admixing with 0.3
mL of 18/35 mesh alpha alumina, an inert diluent. This mixture of solids
was then tested by the procedure described hereinabove. Initially, the
catalyst was conditioned for 3/4 hour at 300.degree. C. under nitrogen,
and for 3/4 hour at 500.degree. C. under nitrogen.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and an ethanol flow of 0.00234 mL/min the results were:
Conversion of ethanol 93%
Selectivity to ethylene 66%
Selectivity to acetaldehyde 18%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and a 2-butanol flow of 0.00234 mL/min the results were:
Conversion of 2-butanol 100%
Selectivity to C.sub.4 olefins 89%
EXAMPLE 11
Another example of crystalline erbium aluminum borate was prepared as
follows: Boric acid (25.7 g, 0.416 mol) dissolved in 94 mL hot deionized
water, PHF alumina sol (194.3 g of 8.2% alumina, 0.156 mol) and
Er(NO.sub.3).sub.3 -5H.sub.2 O (46.1 g, 0.104 mol) were placed into a
blender. The aqueous mixture was blended at a low setting, and 9 mL
ammonium hydroxide was added to the mixture to form a gel. After further
blending for several minutes the gel was air-dried, vacuum-dried for 48
hours (0.3 atm, 120.degree. C.), and calcined according to the following
program:
##STR6##
Analysis of this crystalline erbium aluminum borate by powder X-ray
diffraction found about 60 percent Er.sub.2 O.sub.3 .multidot.2 Al.sub.2
O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about 40 percent Er.sub.2 O.sub.3
.multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3. The BET surface
area of this material was determined to be 0.8 m.sup.2 /g.
EXAMPLE 12
A 1.06 g sample of crystalline erbium aluminum borate from Example 11
(18-35 mesh powder) was prepared ing as a catalyst by mixing with 0.3 mL
of 18/35 mesh alpha alumina, an inert diluent. This mixture of solids was
then tested by the procedure described hereinabove. Initially, the
catalyst was conditioned for one hour at 300.degree. C. under nitrogen,
and for one hour at 500.degree. C. under nitrogen.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and an ethanol flow of 0.00234 mL/min the results were:
Conversion of ethanol 100%
Selectivity to ethylene 96%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and a 2-butanol flow of 0.00234 mL/min the results were:
Conversion of 2-butanol 100%
Selectivity to C4 olefins 98%
EXAMPLE 13
A crystalline holmium aluminum borate was prepared as follows: Boric acid
(47.6 g, 0.771 mol) dissolved in 240 mL of warm deionized water, PHF
alumina sol (207.8 g of 9.5% alumina, 0.193 mol) and Ho(NO.sub.3).sub.3
-5H .sub.2 O dissolved in 45 mL of warm deionized water were placed into a
blender. The mixture was blended at a low setting to obtain a thin pink
gel. The pH of the gel measured 2.1. Upon addition of 20 mL ammonium
hydroxide and subsequent blending, the mixture became somewhat thicker and
the pH measured 4.2. Addition of another 20 mL of ammonium hydroxide and
subsequent blending resulted in a thick light pink gel. The pH of the
final gel measured 6. The gel was air-dried, vacuum-dried for 20 hours
(0.3 atm, 120.degree. C.) to a weight of 110.3 g, and calcined using the
following program:
##STR7##
The pink calcined material emitted fluorescence when illuminated by U.V.
Analysis of this holmium aluminum borate by powder X-ray diffraction found
about 85 percent Er.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4
B.sub.2 O.sub.3 and about 15 percent Er.sub.2 O.sub.3 .multidot.3 Al.sub.2
O.sub.3 .multidot.4 B.sub.2 O.sub.3. The powder X-ray diffraction lines
are set out below:
______________________________________
XRD Lines for Example 13
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.16 VW 6
4.55 W 14
4.34 VW 10
3.92 VW 4
3.61 VS 100
3.48 W 16
3.28 M 27
2.97 VS 96
2.66 W 18
2.61 M 42
2.40 M 40
2.26 M 33
2.20 W 18
1.97 S 55
1.92 M 27
1.81 S 69
1.78 W 12
1.73 VW 8
1.60 VW 8
1.48 VW 10
1.46 VW 9
1.42 W 23
1.41 W 19
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
A second portion was calcined using the following program:
##STR8##
Analysis of this crystalline holmium aluminum borate by powder X-ray
diffraction pattern of high crystallinity found about 10 percent Ho.sub.2
O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about
90 percent Ho.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3 .multidot.4
B.sub.2 O.sub.3.
EXAMPLE 14
A crystalline yttrium aluminum borate was prepared as follows: A hot
solution of boric acid (32.8 g, 0.54 mol, mina sol (174.1 g of a 8.2%
alumina sol, 0.14 mol) in a Waring blender while mixing. To this was added
a hot solution containing 53.6 g of Y(NO.sub.3).sub.3 -6H.sub.2 O (53.6 g,
0.14 mol) in 15 mL of distilled water. After thorough mixing, 20 ml of
ammonium hydroxide solution (1:1 concentrated NH40H and distilled water)
was added to obtain a gel. Mixing was continued until a smooth and uniform
white gel was obtained. The gel was air-dried, vacuum-dried at 120.degree.
C., and pre-calcined to 400.degree. C. A portion of the dry material was
calcined at 975.degree. C. The calcined material emitted fluorescence when
illuminated by U.V. Analysis of this crystalline yttrium aluminum borate
by powder X-ray diffraction pattern of high crystallinity found about 55
percent Y.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot. 4 B.sub.2
O.sub.3 and about 45 percent Y.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3
.multidot.4 B.sub.2 O.sub.3. The powder X-ray diffraction lines are set
out below:
______________________________________
XRD Lines for Example 14
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.17 VW 8
5.37 W 16
4.58 W 16
4.38 S 49
3.62 S 92
3.51 M 30
3.28 S 81
3.18 W 24
2.99 S 73
2.69 S 81
2.62 VS 100
2.41 W 22
2.33 M 27
2.28 W 16
2.13 W 16
2.04 W 16
1.98 W 24
1.90 M 35
1.82 S 65
1.81 M 32
1.74 W 24
1.64 M 43
1.43 W 24
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
EXAMPLE 15
A small portion of the powder was examined for second harmonic generation
efficiency using a Q-switched mode locked YAG laser operating at 1060 nm.
Green light was observed from most of the crystals, which was bright in
spots. This indicates the frequency doubling character of the crystals.
EXAMPLE 16
A crystalline yttrium aluminum borate was prepared using an yttria sol as
follows: Boric acid (13.9 g, 0.22 mol) dissolved in 182 mL warm deionized
water, PHF alumina sol (196.2 g of 7.8% alumina, 0.15 mol) and Y.sub.2
O.sub.3 sol obtained as an experimental sample of PQ Co. (17.0 g of 14.1%
yttria, 0.011 mol) were placed into a blender. The mixture was blended at
a low setting and 28 mL ammonium hydroxide was added to obtain a gel. The
gel was airdried, vacuum-dried overnight (0.3 atm, 106.degree. C.) to a
weight of 34.8 g and calcined using the following program:
##STR9##
The calcined material weighed 22.8 g and had a BET surface area of less
than 1 m.sup.2 /g. Analysis of this crystalline yttrium aluminum borate by
powder X-ray diffraction pattern of high crystallinity found about 40
percent Y.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2
O.sub.3 and about 60 percent Y.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3
.multidot.4 B.sub.2 O.sub.3.
EXAMPLE 17
Another example of crystalline yttrium aluminum borate was prepared as
follows: Boric acid (41.2 g, 0.67 (392.2 g of 7.8% alumina, 0.30 mol) and
yttrium nitrate hexahydrate (25.5 g, 0.067 mol) dissolved in 30 mL warm
deionized water were placed into a blender. The mixture was blended for
about two minutes. Ammonium hydroxide, 10 mL, was added followed by two
minutes of blending and a second addition of ammonium hydroxide, 15 mL,
followed by another one minute of blending the mixture to obtain gel
formation. The gel was air-dried to a weight of 110.0 g. A 75 g portion of
the sample was vacuum-dried for 17 hours at 120.degree. C. and 0.3 atm to
obtain a dry solid material which weighed 58.6 g. A 15.0 g portion of the
dry solid material was calcined according to the following program:
##STR10##
The calcined material weighed 12.0 g and its BET surface area measured 11
m.sup.2 g with a pore volume of 0.052. Analysis of this crystalline
yttrium aluminum borate by powder X-ray diffraction pattern of high
crystallinity found about 60 percent Y.sub.2 O.sub.3 .multidot.2 Al.sub.2
O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about 40 percent Y.sub.2 O.sub.3
.multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3.
EXAMPLE 18
Another example of crystalline yttrium aluminum borate was prepared as
follows: Into a blender are placed boric acid (30.65 g, 0.50 mol) and
yttrium nitrate hexahydrate (47.5 g, 0.124 mol) dissolved in 111 mL hot
distilled water, and alumina sol (243.2 g of 7.8% alumina, 0.186 mol). To
this was added 7 mL conc. NH.sub.4 OH with blending. The resulting gel was
air-dried and a portion of the dry gel was calcined as follows:
##STR11##
Analysis of this crystalline yttrium aluminum borate by powder X-ray
diffraction pattern of high crystallinity found about 40 percent Y.sub.2
O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about
60 percent Y.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3 .multidot.4
B.sub.2 O.sub.3. The surface area of the calcined material was 1 m.sup.2
/g.
EXAMPLE 19
A 0.91 g sample of crystalline yttrium aluminum borate from Example Y-5
(18-35 mesh powder) was prepared for testing as a catalyst by admixing
with 0.1 mL of 18/35 mesh alpha alumina, an inert diluent. This mixture of
solids was then tested by the procedure described hereinabove. At a
temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of0.097
mL/sec, and an ethanol flow of 0.00234 mL/min the results were:
Conversion of ethanol 100%
Selectivity to ethylene 96%. At a temperature of 500.degree. C., a gas flow
(8% oxygen in nitrogen) of 0.097 mL/sec, and a 2-butanol flow of 0.00234
mL/min the results were:
Conversion of 2-butanol 99.5%
Selectivity to C.sub.4 olefins 98.5%. At a temperature of 600.degree. C., a
gas flow (8% oxygen in nitrogen) of 0.097 mL/sec and a propane flow of
0.017 mL/sec, the results were:
Conversion of propane 32%
Selectivity to propene 46%
EXAMPLE 20
A crystalline dysprosium aluminum borate was prepared as follows: A hot
solution of boric acid (32.8 g, 0.54 mol, a 10% excess) in 200 mL
distilled water was added to alumina sol (149.3 g of an 8.2% alumina sol,
distilled water was added to alumina sol (149.3 g of an 8.2% alumina sol,
solution containing Dy(NO.sub.3).sub.3 -5H.sub.2 O (52.7 g, 0.12 mol) in
15 mL of distilled water. After thorough mixing, 15 mL of dilute (1:1)
nitric acid was added to obtain a homogeneous gel. Mixing was continued
until a smooth and uniform off-white gel was obtained. The gel was
air-dried, vacuum-dried at 400.degree. C. and a portion of the dry
material was calcined at 975.degree. C. Analysis of this crystalline
dysprosium aluminum borate by powder X-ray diffraction pattern of high
crystallinity found about 50 percent Dy.sub.2 O.sub.3 .multidot.2 Al.sub.2
O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about 50 percent Dy.sub.2 O.sub.3
.multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3. The powder X-ray
diffraction lines of the crystalline dysprosium aluminum borate are set
out below:
______________________________________
XRD Lines for Example 20
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.20 W 17
5.39 M 39
4.64 M 30
4.59 W 17
4.42 M 26
3.62 VS 97
3.52 S 57
3.28 S 57
2.99 S 57
2.80 M 30
2.69 VS 100
2.64 S 52
2.42 W 22
2.33 M 43
2.13 M 26
1.98 W 17
1.92 W 17
1.90 M 35
1.83 M 30
1.76 W 17
1.64 W 22
1.63 W 22
1.43 M 39
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
EXAMPLE 21
A small portion of the powder was examined for second harmonic generation
efficiency using a Q-switched mode locked YAG laser operating at 1060 nm.
Green light was observed from most of the crystals, which was bright in
spots. This indicates the frequency doubling character of the crystals.
EXAMPLE 22
A crystalline dysprosium aluminum borate was prepared as follows: Boric
acid (38.6 g, 0.62 mol) dissolved in 140 mL hot deionized water, PHF
alumina sol (120.6 g of 6.6% alumina, 0.78 mol) and Dy(NO.sub.3).sub.3
-5H.sub.2 O (45.6 g, 0.104 mol) dissolved in 140 mL deionized water were
placed into a blender. The mixture was blended at a low setting, and 131
mL ammonium hydroxide was added to obtain a very thin gel. The gel was
air-dried, vacuum-dried (0.3 atm, 110.degree. C.), and calcined according
to the following program:
##STR12##
Analysis of this crystalline dysprosium aluminum borate by powder X-ray
diffraction pattern of high crystallinity found about 60 percent Dy.sub.2
O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about
40 percent Dy.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3 .multidot.4
B.sub.2 O.sub.3.
EXAMPLE 23
A 0.98 g sample of crystalline dysprosium aluminum 30 borate from Example
22 (18-35 mesh powder) was prepared for testing as a catalyst by admixing
with 0.3 mL of 18/35 mesh alpha alumina, an inert diluent. This mixture of
solids was then tested by the procedure described hereinabove. Initially,
the catalyst was conditioned for 3/4 hour at 300.degree. C. under
nitrogen, and for 3/4 hour at 500.degree. C. under nitrogen.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and an ethanol flow of 0.00234 mL/min, the results were:
Conversion of ethanol 94%
Selectivity to ethylene 72%. At a temperature of 500.degree. C., a gas flow
(8% oxygen in nitrogen) of 0.097 mL/sec, and a 2-butanol flow of 0.00234
mL/min, we obtained the following results:
Conversion of 2-butanol 100%
Selectivity to C.sub.4 olefins 87%
EXAMPLE 24
A crystalline dysprosium aluminum borate was prepared as follows: Into a
blender is placed boric acid (10.4 g, 0.17 mol) dissolved in 38 mL hot
deionized water, PHF alumina sol (519.3 g of 6.6% alumina, 0.34 mol) and
Dy(N.sub.3).sub.3 -5H.sub.2 O (24.6 g, 0.056 mol) dissolved in 38 mL
deionized water. The mixture was blended at a low setting, and 11 mL
ammonium hydroxide was added. The solution became so thick that another 10
mL of water was added. The mixture was stirred and blended for several
minutes. The gel was removed and placed on a 35 cm.times.45 cm plastic
tray for drying. The solid was placed in a vacuum oven for 48 hours (0.3
atm, 120.degree. C.). The material was calcined at 930.degree. C.
The white crystalline dysprosium aluminum borate had a BET surface area of
25 m.sup.2 /g. Analysis of this crystala line dysprosium aluminum borate
by powder X-ray diffraction pattern of high crystallinity found about 10
percent Dy.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2
O.sub.3 and about 90 percent Dy.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3
.multidot.4 B.sub.2 O.sub.3.
EXAMPLE 25
A 0.56 g sample of crystalline dysprosium aluminum borate from Example 24
(18-35 mesh powder) was prepared for testing as a catalyst by admixing
with 0.3 mL of 18/35 mesh alpha alumina, an inert diluent. This mixture of
solids was then tested by the procedure described hereinabove. Initially,
the catalyst was conditioned for one hour at 300.degree. C. under
nitrogen, and for one hour at 500.degree. C. under nitrogen.
At a temperature of 600.degree. C., a gas flow (8% oxygen in nitrogen) of
0.109 mL/sec, and a propane flow of 0.0094 mL/sec, the results were:
Conversion of propane 14%
Selectivity to propene 44%. At a temperature of 500.degree. C., a gas flow
(8% oxygen in nitrogen) of 0.109 mL/sec, and an ethanol flow of 0.00234
mL/min, the results were:
Conversion of ethanol 77%
Selectivity to ethylene 40%
Selectivity to acetic acid 10%. At a temperature of 400.degree. C., a gas
flow (8% oxygen in nitrogen) of 0.109 mL/sec, and a 2-butanol flow of
0.00234 mL/min, the results were:
Conversion of 2-butanol 99%
Selectivity to C.sub.4 olefins 100%. At a temperature of 600.degree. C., a
gas flow (8% oxygen in nitrogen) of 0.109 mL/sec, an ammonia flow of 0.013
mL/min, and a toluene flow of 0.00234 mL/min, the results were:
Conversion of toluene 25%
Selectivity to benzonitrile 87%. At a temperature of 600.degree. C., a gas
flow (nitrogen) of 0.200 mL/sec, and a liquid cumene flow at 0.00328
mL/min, the results were:
Conversion of cumene 17%
Selectivity to alpha methylstyrene 95%
A crystalline terbium aluminum borate was prepared as follows: Boric acid
(28.4 g, 0.46 mol) dissolved in 150 mL warm deionized water, PHF alumina
sol (131.2 g of 8.9% alumina, 0.114 mol) and Tb(NO.sub.3).sub.3 -6H.sub.2
O dissolved in 250 mL of warm deionized water were placed into a blender.
The aqueous mixture was blended forming a thin gel, the pH of which
measured 4. After 9 mL of ammonium hydroxide was added to the mixture a
thick gel formed the pH of which measured 5. The gel was air-dried, and
vacuum-dried for 6 hours (0.3 atm, 120.degree. C.). The dried material,
79.6 g, was heated in air at 400.degree. C. for 6 hours and was calcined
according to the following program:
##STR13##
Analysis of this crystalline terbium aluminum borate by powder X-ray
diffraction pattern of high crystallinity found about 10 percent Tb.sub.2
O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3.
A second portion of the dry material was calcined according to the
following program:
##STR14##
The BET surface area of the calcined material was determined to be 0.8
m2/g. Analysis of this crystalline dysprosium aluminum borate by powder
X-ray diffraction pattern of high crystallinity found about 75 percent
Tb.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3
and about 25 percent Tb.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3
.multidot.4 B.sub.2 O.sub.3.
The powder X-ray diffraction lines for the resulting crystalline terbium
aluminum borate are set out below:
______________________________________
XRD Lines for Example 26
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.42 W 16
4.98 VW 6
4.65 W 16
4.45 VW 8
4.03 VW 7
3.98 VW 8
3.65 VS 100
3.55 M 28
3.33 W 23
3.01 S 70
2.82 VW 8
2.71 M 32
2.66 M 27
2.43 W 22
2.33 W 10
2.29 W 18
2.22 VW 11
2.05 W 14
1.99 W 21
1.94 W 14
1.84 M 36
1.82 W 20
1.47 VW 7
1.43 VW 8
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
EXAMPLE 27
A crystalline gadolinium aluminum borate was prepared as follows: A hot
solution of boric acid (32.8 g, 0.54 mol, a 10% excess) in 200 mL
distilled water was added to alumina sol (149.3 g of a 8.2% alumina sol,
0.12 mol) in a Waring blender while mixing. To this was added a hot
solution containing Gd(NO.sub.3).sub.3 -5H.sub.2 O (52.0 g, 0.12 mol) in
15 mL of distilled water. After thorough mixing, a homogeneous gel formed
the pH of which measured 3. Mixing was continued until a smooth and
uniform white product was obtained. The gel was air-dried,vacuum-dried at
120.degree. C. and pre-calcined to 400.degree. C. A portion of this
material was calcined at 900.degree. C. The calcined material emitted
fluorescence when illuminated by U.V. Analysis of this crystalline
gadolinium aluminum borate by powder X-ray diffraction pattern of high
crystallinity found about 90 percent Gd.sub.2 O.sub.3 .multidot.2 Al.sub.2
O.sub.3 .multidot.4 B.sub.2 O.sub. 3 and about 10 percent Gd.sub.2 O.sub.3
.multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3.
The powder X-ray diffraction lines for the resulting crystalline gadolinium
aluminum borate are set out below:
______________________________________
XRD Lines for Example 27
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.25 M 41
5.41 VW 8
4.94 VW 9
4.61 W 23
3.96 W 15
3.64 VS 100
3.33 VW 8
3.00 S 64
2.43 W 23
2.80 VW 8
2.71 VW 11
2.70 W 13
2.66 VW 8
2.28 W 19
2.22 VW 10
2.04 VW 10
1.99 W 19
1.98 W 16
1.93 W 13
1.83 W 20
1.82 VW 12
1.50 VW 5
1.43 VW 8
1.42 VW 8
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
A small portion of the powder was examined for second harmonic generation
efficiency using a Q-switched mode locked YAG laser operating at 1060 nm.
Green light was observed from most of the crystals, which was bright in
spots. This indicates the frequency doubling character of the crystals.
EXAMPLE 29
Another example of crystalline gadolinium aluminum borate was prepared as
follows: Boric acd (26.1 g, 0.35 mol) dissolved in 110 mL hot deionized
water, PHF alumina sol (206.7 g of 7.8% alumina, 0.158 mol) and
Gd(NO.sub.3).sub.3 -.sub.5 H.sub.2 O (45.7 g, 0.106 mol) dissolved in 50
mL deionized water were placed into a blender. The mixture was blended at
a low setting, and 18 mL ammonium hydroxide was added to obtain a gel
which was blended for several minutes. The gel was air-dried, vacuum-dried
for one week (0.3 atm, 110.degree. C.), and calcined using the following
program:
##STR15##
Analysis of this very light pink gadolinium aluminum borate by powder X-ray
diffraction pattern of high crystallinity found about 10 percent Gd.sub.2
O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about
90 percent Gd.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3 .multidot.4
B.sub.2 O.sub.3. The BET surface area of the calcined material measured
8.7 m.sup.2 /g.
EXAMPLE 30
A 1.09 g sample of crystalline gadolinium aluminum borate from Example 29
(18-35 mesh powder) was prepared for testing as a catalyst by admixing
with 0.3 mL of 18/35 mesh alpha alumina, an inert diluent. This mixture of
solids was then tested by the procedure described hereinabove. Initially,
the catalyst was conditioned for one hour at 300.degree. C. under
nitrogen, and for one hour at 500.degree. C. under nitrogen.
At a temperature of 600.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and a propane flow of 0.094 mL/sec, the results were:
Conversion of propane 44%
Selectivity to propene 43%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and an ethanol flow of 0.00234 mL/min, the results were:
Conversion of ethanol 98%
Selectivity to acetaldehyde 32%
Selectivity to ethylene 50%
At a temperature of 600.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and a 2-butanol flow of 0.00234 mL/min, the results were:
Conversion of 2-butanol 100%
Selectivity to methyl ethyl ketone 25%
Selectivity to C.sub.4 olefins 69%
At temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.321 mL/sec, and an ammonia flow of 0.013 mL/min, and a liquid toluene
flow of 0.00234 mL/min, the results were:
Conversion of toluene 15%
Selectivity to benzonitrile 87%
EXAMPLE 31
A crystalline europium aluminum borate was prepared as follows: Boric acid
(21.3 g, 0.344 mol) dissolved in 110 mL warm deionized water, PHF alumina
sol (93.3 g of (5% alumina, 0.087 mol) and Eu(NO.sub.3).sub.3 -6H.sub.2 O
dissolved in 35 mL of warm deionized water were placed into a blender. The
mixture was blended at a low setting to obtain a thin gel. The pH of this
gel measured 4. Upon addition of 8 mL ammonium hydroxide and subsequent
blending, the mixture became a thick gel. The final pH of the gel measured
6. The gel was removed and placed onto a 35 cm.times.45 cm plastic tray
and air-dried. The solid (51.3 g) was placed into a vacuum oven overnight
(0.3 atm, 106.degree. C.). The vacuum-dried solid material weighed 41.6 g.
A 13.0 g portion of the material was calcined using the following program:
##STR16##
The calcined material weighed 7.51 g. Analysis of this europium aluminum
borate by powder X-ray diffraction pattern of high crystallinity found
about 80 percent Eu.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4
B.sub.2 O.sub.3 and about 20 percent Eu.sub.2 O.sub.3 .multidot.3 Al.sub.2
O.sub.3 .multidot.4 B.sub.2 O.sub.3.
A second portion (7.50 g) was calcined using the following program:
##STR17##
This calcined material weighs 6.16 g and emitted fluorescence when
illuminated by U.V. Analysis of this europium aluminum borate by powder
X-ray diffraction pattern of high crystallinity found about 100 percent
Eu.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3.
The powder X-ray diffraction lines for the resulting crystalline europium
aluminum borate are set out below:
______________________________________
XRD Lines for Example 31
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.22 VW 3
4.60 W 15
3.94 VW 11
3.62 VS 100
2.99 S 89
2.42 M 32
2.27 M 28
2.20 W 13
1.98 M 37
1.97 M 29
1.92 M 26
1.82 M 41
1.81 M 28
1.53 VW 5
1.49 VW 8
1.47 VW 12
1.43 W 17
1.42 W 16
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
EXAMPLE 32
A crystalline samarium aluminum borate was prepared as follows: A hot
solution of boric acid (32.8 g, 0.54 mol, a 10% excess) in 200 mL
distilled water was added to alumina sol (149.3 g of an 8.2% alumina sol,
0.12 mol) in a Waring blender while mixing. A hot solution of
Sm(NO.sub.3).sub.3 -5H.sub.2 O (51.1 g, 0.12 mol) in 15 mL of distilled
water was added to the mixture. After thorough mixing, the gel was
sufficiently thick that no ammonium hydroxide was added. Mixing was
continued until a smooth and uniform pale yellow product was obtained. The
pH of the gel was 3. The gel was air-dried, vacuum-dried 120.degree. C.,
and precalcined to 400.degree. C. A portion of this material was calcined
at 975.degree. C. The calcined material emitted fluorescence when
illuminated by U.V. Analysis of this very light pink gadolinium aluminum
borate by powder X-ray diffraction pattern of high crystallinity found
about 70 percent Sm.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4
B.sub.2 O.sub.3 and about 30 percent Sm.sub.2 O.sub.3 .multidot.3 Al.sub.2
O.sub.3 .multidot.4 B.sub.2 O.sub.3. The powder X-ray diffraction lines of
this crystalline samarium aluminum borate are set out below:
______________________________________
XRD Lines for Example 32
Interplanar
Spacing d,.sup.1
Assigned Relative
.ANG. Strength.sup.2
Intensity
______________________________________
9.34 .+-. 0.25 W 19
4.64 .+-. 0.15 W 20
3.96 .+-. 0.10 VW 10
3.64 .+-. 0.10 VS 100
3.01 .+-. 0.10 S 71
2.43 .+-. 0.08 W 23
2.28 .+-. 0.05 W 15
2.22 .+-. 0.05 VW 6
2.05 .+-. 0.04 VW 9
1.97 .+-. 0.04 VW 9
1.93 .+-. 0.04 VW 11
1.83 .+-. 0.04 W 19
______________________________________
.sup.1 Angstroms
.sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong
EXAMPLE 33-2
A small portion of the powder was examined for second harmonic generation
efficiency using a Q-switched mode locked YAG laser operating at 1060 nm.
Green light was observed from most of the crystals, which was bright in
spots. This indicates the frequency doubling character of the crystals.
EXAMPLE 34
A crystalline neodymium aluminum borate was prepared as follows: Boric acid
(32.8 g, 0.531 mol, a 10% excess) dissolved in 200 mL warm deionized
water, PHF alumina sol (149.3 g of 8.2% alumina, 0.12 mol) and Nd(NO.sub.6
3).sub.3 -5H.sub.2 O (50.4 g, 0.12 mol) dissolved in 100 mL deionized
water were placed into a blender. The mixture was blended at a low
setting. Upon setting the mixture became a thick lavender gel which was
air-dried, and vacuum-dried (0.3 atm, 100.degree. C.) overnight to obtain
a dry solid.
EXAMPLE 35
A first portion of the dry solid from Example 34 was calcined at
975.degree. C. in air. The calcined material emitted fluorescence when
illuminated by U.V. Analysis of the resulting crystalline neodymium
aluminum borate by powder X-ray diffraction pattern found about 90 percent
Nd.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3
and about 10 percent Nd.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3
.multidot.4 B.sub.2 O.sub.3.
A 0.68 g sample (18-35 mesh powder) of this crystalline neodymium aluminum
borate was prepared for testing as a catalyst by admixing with 0.3 mL of
18/35 mesh alpha alumina, an inert diluent. This mixture of solids was
then tested by the procedure described hereinabove. Initially, the
catalyst was conditioned for 45 minutes at 300.degree. C. under a stream
of nitrogen.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.109 mL/sec, and an ethanol flow of 0.00234 mL/min, the results were:
Conversion of ethanol 88%
Selectivity to ethylene 77%
EXAMPLE 36
A second portion of the dry solid from Example 43 was calcined at
1150.degree. C. Analysis of the resulting crystalline neodymium aluminum
borate by powder X-ray diffraction pattern found about 100 percent
Nd.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3.
A sample of this calcined material was prepared for catalytic studies as
described above in Example 35.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.109 mL/sec, and an ethanol flow of 0.00234 mL/min, the results were:
Conversion of ethanol 63%
Selectivity to acetaldehyde 75%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.109 mL/sec, and a 2-butanol flow at 0.00234 mL/min, the results were:
Conversion of 2-butanol 66%
Selectivity to methyl ethyl ketone 77%
These data demonstrate significant chemical differences between material
containing crystalline (Nd.sub.2 O.sub.3).multidot.2(Al.sub.2
O.sub.3).multidot.4(B.sub.2 O.sub.3) and material containing crystalline
(Nd.sub.2 O.sub.3).multidot.3(Al.sub.2 O.sub.3)4(B.sub.2 O.sub.3).
EXAMPLE 37
Another portion of the crystalline (Nd.sub.2 O.sub.3).multidot.2(Al.sub.2
O.sub.3).multidot.4(B.sub.2 O.sub.3) from Example 35 was treated with warm
nitric acid diluted with water (1:1) and dried. This dry material was
prepared for catalytic studies as described above in Example 35 above.
At a temperature of 500.degree. C., a gas, flow (8% oxygen in nitrogen) of
0.109 mL/sec, and an ethanol flow at 0.00234 mL/min, the results were:
Conversion of ethanol 85%
Selectivity to acetaldehyde 68%
EXAMPLE 38
A portion of the crystalline (Nd.sub.2 O.sub.3).multidot.3(Al.sub.2
O.sub.3).multidot.4(B.sub.2 O.sub.3) from Example 36 was treated with warm
nitric acid as described in Example 37 above and prepared for catalytic
studies as described above in Example 35.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.109 mL/sec, and an ethanol flow at 0.00234 mL/min, the results were:
Conversion of ethanol 50%
Selectivity to acetaldehyde 73%
EXAMPLE 39
A small portion of the crystalline (Nd.sub.2 O.sub.3).multidot.2(Al.sub.2
O.sub.3).multidot.4(B.sub.2 O.sub.3) from Example 35 was leached with warm
nitric acid as described in Example 37 above and examined for second
harmonic generation efficiency using a Q-switched mode locked YAG laser
operating at 1060 nm. Green light was observed from most of the crystals.
This indicates the frequency-doubling character of the crystals.
EXAMPLE 40
Another crystalline neodymium aluminum borate example was prepared as
follows: Boric acid (40.2 g, 0.65 mol) dissolved in 200 mL warm deionized
water, PHF alumina sol (319 g of 7.8% alumina, 0.243 mol) and
Nd(NO.sub.3).sub.3 -5H.sub.2 O (68.3 g, 0.163 mol) dissolved in 100 mL
deionized water were placed into a blender. The mixture was blended at a
low setting and 25 mL of warm concentrated ammonium hydroxide was added.
While the mixture was stirred and blended for several minutes the mixture
became a thick gel. The gel was air-dried, and then vacuum-dried (0.3 atm,
110.degree. C.) overnight.
EXAMPLE 41
A first portion of the dry material from Example 40 was calcined using the
following program:
##STR18##
The BET surface area of this calcined material measured 0.5 m.sup.2 /g.
Analysis of the resulting crystalline neodymium aluminum borate by powder
X-ray diffraction pattern found about 30 percent Nd.sub.2 O.sub.3
.multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3 and about 70
percent Nd.sub.2 O.sub.3 .multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2
O.sub.3.
A 1.02 g sample (18-35 mesh powder) the crystalline neodymium aluminum
borate was prepared for testing as a catalyst by mixing with 0.3 mL of
18/35 mesh alpha alumina, an inert diluent. This mixture of solids was
then tested by the procedure described hereinabove. Initially, the
catalyst was conditioned under nitrogen at 300.degree. C. for one hour and
at 500.degree. C. for one hour.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.101 mL/sec, and an ethanol flow of 0.00234 mL/min, the results were:
Conversion of ethanol 75%
Selectivity to acetaldehyde 42%
Selectivity to ethylene 43%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.101 mL/sec, and a 2-butanol flow at 0.00234 mL/min, the results were:
Conversion of 2-butanol 100%
Selectivity to C.sub.4 olefins 67%
At a temperature of 650.degree. C., a gas flow (nitrogen) of 0.200 mL/sec,
and a liquid cumene flow at 0.00328 mL/min, the results were:
Conversion of cumene 19%
Selectivity to alpha-methylstyrene 48%
EXAMPLE 42
A second portion of the dry material from Example 40 was calcined to
1220.degree. C. The resulting crystalline neodymium aluminum borate was
analyzed by its powder X-ray diffraction pattern which indicated a pure
(Nd.sub.2 O.sub.3).multidot.3(Al.sub.2 O.sub.3).multidot.4(B.sub.2
O.sub.3) was obtained. The BET surface area decreased to below 0.2 m.sup.2
/g. A 0.95 g sample of this pure (Nd.sub.2 O.sub.3).multidot.3(Al.sub.2
O.sub.3).multidot.4(B.sub.2 O.sub.3) was screened for catalytic activity
described in Example 8 above.
At a tepperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and an ethanol flow of 0.00234 mL/min, the results were:
Conversion of ethanol 55%
Selectivity to acetaldehyde 77%
At a temperature of 600.degree. C., a gas flow (nitrogen) of 0.200 mL/sec,
and a liquid cumene flow at 0.00328 mL/min, the results were:
Conversion of cumene 2%
Selectivity to alpha-methylstyrene 67%
EXAMPLE 43
A crystalline praseodymium aluminum borate was prepared as follows: Into a
blender is placed boric acid (27.0 g, 0.437 mol) dissolved in 130 mL warm
deionized water, PHF alumina sol (214.2 g of 7.8% alumina, 0.164 mol) and
Pr(NO.sub.3).sub.3 -5H.sub.2 O (46.1 g, 0.109 mL deionized water. The
mixture was blended at a low setting, and 12 mL ammonium hydroxide was
added. The solution became thick and the mixture was stirred and blended
for several minutes. The gel was air-dried, and then vacuum-dried for 48
hours (0.3 atm, 120.degree. C.). The dry material calcined using the
following program:
##STR19##
The resulting solid material emitted fluorescence when illuminated by U.V.
This crystalline praseodymium aluminum borate was analyzed by its powder
X-ray diffraction pattern to contain pure crystalline (Pr.sub.2
O.sub.3).multidot.2(Al.sub.2 O.sub.3).multidot.4(B.sub.2 O.sub.3).
EXAMPLE 44
A 0.93 g sample (18-35 mesh powder) of the above compound was prepared for
testing as a catalyst by admixing with 0.3 mL of 18/35 mesh alpha alumina,
and inert diluent. This mixture of solids was then tested by the procedure
described hereinabove. Initially, the catalyst was conditioned under
nitrogen for one hour at 300.degree. C., followed by an additional hour at
500.degree. C.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.109 mL/sec, and an ethanol flow at 0.00234 mL/min, the results were:
Conversion of ethanol 95%
Selectivity to ethylene 67%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.109 mL/sec, and a 2-butanol flow of 0.00234 mL/min, the results were:
Conversion of 2-butanol 100%
Selectivity to C.sub.4 olefins 90%
EXAMPLE 45
Another example of a crystalline praseodymium aluminum borate was prepared
as follows: A hot solution of boric acid (32.8 g, 0.54 mol, a 10% excess)
in 200 mL distilled water was added to alumina sol (149.3 g of an 8.2%
alumina sol, 0.12 mol) in a Waring blender while mixing. A hot solution of
Pr(NO.sub.3).sub.3 -5H.sub.2 O (50.0 g, 0.12 mol) in 15 mL of deionized
water was added to the mixture. Mixing was continued until a smooth and
uniform sea-green gel was obtained. The gel was air-dried, vacuum-dried,
and precalcined to 400.degree. C. A portion of this material was calcined
at 900.degree. C. The material was characterized by X-ray diffraction in
which the (Pr.sub.2 O.sub.3).multidot.2(Al.sub.2
O.sub.3).multidot.4(B.sub.2 O.sub.3) phase was identified.
EXAMPLE 46
A small portion of the crystalline (Pr.sub.2 O.sub.3).multidot.2Al.sub.2
O.sub.3).multidot.4(B.sub.2 O.sub.3) from Example 45 was examined for
second harmonic generation efficiency using a Q-switched mode locked YAG
laser operating at 1060 nm. Green light was observed from most of the
crystals.
EXAMPLE 47
A crystalline cerium aluminum borate having an X-ray diffraction pattern
comprising significant lines substantially as described in Table I was
prepared as follows: Boric acid (40.6 g, 0.657 mol) dissolved in 200 mL
warm deionized water, PHF alumina sol (321.7 g of 7.8% alumina, 0.246 mol)
and Ce(NH.sub.4).sub.2 (NO.sub.3).sub.6 (89.9 g, 0.164 mol) dissolved in
100 mL deionized water were placed into a blender. While the mixture was
blended at a low setting, 25 mL of ammonium hydroxide was added. As the
mixture was stirred and blended for several minutes, it became a thick
gel. The gel was air-dried, vacuum-dried (0.3 atm, 110.degree. C.)
overnight, and calcined using the following program:
##STR20##
The material resulting from this calcination was amorphous. A portion of
the amorphous material was further calcined at 1020.degree. C. for 8 hours
to obtain a crystalline cerium aluminum borate. Analysis of the resulting
crystalline cerium aluminum borate by powder X-ray diffraction pattern
found about 50 percent Ce.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3
.multidot.4 B.sub.2 O.sub.3 and about 50 percent Nd.sub.2 O.sub.3
.multidot.3 Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3. The BET surface
area of this cerium aluminum borate measured 5.0m.sup.2 /g.
EXAMPLE 48
A 1.09 g sample (18-35 mesh powder) of crystalline cerium aluminum borate
from Example 47 was prepared for testing a catalyst by admixing with 0.3
mL of 18/35 mesh alpha alumina, an inert diluent. This mixture of solids
was then tested by the procedure described hereinabove. Initially, the
catalyst was conditioned nitrogen for one hour at 300.degree. C., and then
at 500.degree. C. under nitrogen for one hour.
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and an ethanol flow of 0.00234 mL/min, the results were:
Conversion of ethanol 66%
Selectivity to acetaldehyde 85%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.097 mL/sec, and a 2-butanol flow of 0.00234 mL/min, the results were:
Conversion of 2-butanol 88%
Selectivity to methyl ethyl ketone 84%
At a temperature of 500.degree. C., a gas flow (8% oxygen in nitrogen) of
0.310 mL/sec, an ammonia flow of 0.013 mL/min, and a liquid toluene flow
of 0.00234 mL/min, the results were:
Conversion of toluene 9%
Selectivity to benzonitrile 57%
EXAMPLE 49
Another crystalline cerium aluminum borate was prepared as follows: A hot
solution of boric acid (32.8 g, 0.54 mol, a 10% excess) in 200 mL
distilled water was added to alumina sol (149.3 g of a 8.2% alumina sol,
0.12 mol) in a Waring blender while mixing. To this was added a hot
solution containing Ce(NH.sub.4).sub.2 (NO.sub.3).sub.6 (65.8 g, 0.12 mol)
in 15 mL of distilled water. After thorough mixing, 20 mL of ammonium
hydroxide solution (1:1 concentrated NH.sub.4 OH and distilled water) was
added to obtain a thin homogeneous gel whose final pH is 4. Mixing was
continued until a smooth and uniform yellow-orange gel was obtained. The
gel was air-dried, vacuum-dried at 120.degree. C., and precalcined to
400.degree. C. A portion of the dry material was calcined at 975.degree.
C. The resulting material emitted fluorescence when illuminated by U.V.
Analysis of the crystalline cerium aluminum borate by powder X-ray
diffraction pattern found 90+ percent Ce.sub.2 O.sub.3 .multidot.2
Al.sub.2 O.sub.3 .multidot.4 B.sub.2 O.sub.3.
EXAMPLE 50
A small portion of the crystalline (Ce.sub.2 O.sub.3).multidot.2(Al.sub.2
O.sub.3).multidot.4(B.sub.2 O.sub.3) from Example 49 was examined for
second harmonic generation efficiency using a Q-switched mode locked YAG
laser operating at 1060 nm. Green light was observed from most of the
crystals, which was bright in spots. This indicates the frequency doubling
character of the crystals.
EXAMPLE 51
A crystalline lanthanum aluminum borate was prepared as follows: A hot
solution of boric acid (32.8 g, 0.54 mol, a 10% excess) in 200 mL
distilled water was added to alumina sol (149.3 g of a 8.2% alumina sol,
0.12 mol) in a Waring blender while mixing. To this was added a hot
solution containing La(NO.sub.3).sub.3 -6H.sub.2 O (52.0 g, 0.12 mol) in
15 mL of distilled water. After thorough mixing, a gel was obtained. The
pH of the gel was 3. Mixing was continued until a smooth and uniform white
product was obtained. The gel was air-dried, vacuum-dried at 120.degree.
C., and pre-calcined to 400.degree. C. A portion of this material was
calcined when illuminated by U.V. Analysis of the crystalline lanthanum
aluminum borate by powder X-ray diffraction pattern found about 100
percent La.sub.2 O.sub.3 .multidot.2 Al.sub.2 O.sub.3 .multidot.4 B.sub.2
O.sub.3.
EXAMPLE552
A small portion of the crystalline (La.sub.2 O.sub.3).multidot.2(Al.sub.2
O.sub.3).multidot.4(B.sub.2 O.sub.3 from Example 51 was examined for
second harmonic generation efficiency using a Q-switched mode locked YAG
laser operating at 1060 nm. Green light was observed from most of the
crystals. This indicates the frequency doubling character of the crystals.
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